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COSTS OF CORROSION
11
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COSTS OF CORROSION
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COSTS OF CORROSION
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COSTS OF CORROSION
EPRI in its research report on the "Cost of Corrosion in the
Electric Power Industry" estimated that the cost of corrosion in
Electrical Industry of USA was of the order of US $ 34.5 Billion per
annum in 2003. Based on the studies various corrosion problems
in the Fossil power plants were identified. Around US $ 11 billion
was due to boiler tube failures followed by US $ 6 billion due to
corrosion problems in turbines
At present no such studies have been conducted for Indian
power sector. However, based on various corrosion related
problems being analyzed by NTPC - R&D and the literature
analysis an attempt is being made to identify the high cost
corrosion related problems where research & development
efforts can be made to provide remedial measures and thereby
reduce O&M costs & forced outages and improve performance.
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COSTS OF CORROSION
Corrosion Problem
Depreciation
Corrosion Cost
US $
Total Corrosion
Cost US $
3,43,50,00,000
1,14,20,00,000
4,57,70,00,000
91,60,00,000
22,84,00,000
1,14,44,00,000
45,80,00,000
14,27,50,000
60,07,50,000
27,48,00,000
8,56,50,000
36,04,50,000
27,48,00,000
8,56,50,000
36,04,50,000
18,32,00,000
14,27,50,000
32,59,50,000
18,32,00,000
2,85,50,000
21,17,50,000
9,16,00,000
5,71,00,000
14,87,00,000
9,16,00,000
5,71,00,000
14,87,00,000
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COSTS OF CORROSION
Corrosion Problem
Depreciation
Corrosion Cost
US $
Total Corrosion
Cost
US $
4,58,00,000
8,56,50,000
13,14,50,000
9,16,00,000
2,85,50,000
12,01,50,000
9,16,00,000
2,85,50,000
12,01,50,000
9,16,00,000
2,85,50,000
12,01,50,000
9,16,00,000
2,85,50,000
12,01,50,000
9,16,00,000
2,85,50,000
12,01,50,000
45,80,00,000
8,56,50,000
54,36,50,000
Total
3,43,50,00,000
1,14,20,00,000
4,57,70,00,000
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COSTS OF CORROSION
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WHAT IS CORROSION
IRON OXIDE
STEEL
REFINING
CORROSION
MILLING
IRON OXIDE
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CORROSION
General Corrosion
Pitting Corrosion
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WHAT IS CORROSION
M2+ + 2e-
ANODIC REACTION
N 2- + 2e
MIC
CATHODIC REACTION
Dezincification
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Corrosion Basics
Corrosion requires:
Oxygen & Water
Rusting takes place
presence of Air & Water
in
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Atmospheric Corrosion
22
Relationship between corrosion rate and the moisture content of air shows the importance of
maintaining relative humidity below about 40%.
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Galvanic Series
(inert)
(active)
more anodic
more cathodic
23
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Galvanic Series
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Galvanic Series
PRACTICAL GALVANIC SERIES
Material
Potential*
Pure Magnesium
-1.75
Magnesium Alloy
-1.60
Zinc
-1.10
Aluminum Alloy
-1.00
Cadmium
-0.80
-0.70
-0.50
Cast Iron
-0.50
Stainless Steel
-0.50 to + 0.10
-0.20
Titanium
-0.20
Gold
+0.20
+0.30
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Reinforced Concrete
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Concrete Deterioration
Durable concrete is defined as concrete fit for the purpose for which it
was intended, under the conditions to which the concrete is expected,
and for the expected life during which the concrete is to remain in
service.
ACI 201.2R Guide to Durable Concrete Durability of hydraulic
cement concrete is determined by its ability to resist weathering action,
chemical attack, abrasion, or any other process of deterioration.
ACI 201 Deterioration Modes Freezing & Thawing, Alkali-Aggregate
Reaction (AAR), Chemical attack, Corrosion of embedded metal,
abrasion
Corrosion is one of the major modes of deterioration of concrete
structures and is considered a big threat to the durability of the
structures especially for structures in contact with water/seawater.
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Concrete Deterioration
S.No Deterioration Mode
1
Structural Failure:
Actual structural failure, or even structural
cracking is only rarely encountered but it
is important to differentiate between
cracking from structural and other
causes.
Typical Appearance
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Concrete Deterioration
S.No Deterioration Mode
Typical Appearance
3
Plastic Shrinkage Cracking: When water evaporates
from the surface of freshly placed concrete faster than it
is replaced by bleed water, the surface concrete shrinks.
Due to the restraint provided by the concrete below the
drying surface layer, tensile stresses develop in the weak,
stiffening plastic concrete, resulting in shallow cracks of
varying depth. These cracks are often fairly wide at the
surface.
4
Drying Shrinkage: Because almost all concrete is mixed
with more water than is needed to hydrate the cement,
much of the remaining water evaporates, causing the
concrete to shrink. Restraint to shrinkage, provided by the
subgrade, reinforcement, or another part of the structure,
causes tensile stresses to develop in the hardened
concrete. Restraint to drying shrinkage is the most
common cause of concrete cracking. In many
applications, drying shrinkage cracking is inevitable.
Therefore, contraction (control) joints are placed in
concrete to predetermine the location of drying shrinkage
cracks.
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Concrete Deterioration
S.No Deterioration Mode
Typical Appearance
5
D-cracking is a form of freeze-thaw deterioration that has
been observed in some pavements after three or more
years of service. Due to the natural accumulation of water
in the base and subbase of pavements, the aggregate
may eventually become saturated. Then with freezing and
thawing cycles, cracking of the concrete starts in the
saturated aggregate at the bottom of the slab and
progresses upward until it reaches the wearing surface.
D-cracking usually starts near pavement joints.
6
Thermal cracks:
Temperature rise (especially significant in mass concrete)
results from the heat of hydration of cementitious
materials. As the interior concrete increases in
temperature and expands, the surface concrete may be
cooling and contracting. This causes tensile stresses that
may result in thermal cracks at the surface if the
temperature differential between the surface and center is
too great. The width and depth of cracks depends upon
the temperature differential, physical properties of the
concrete, and the reinforcing steel.
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Concrete Deterioration
S.No Deterioration Mode
7
Corrosion of Steel:
Steel reinforcement is normally chemically protected
from corrosion by the alkaline nature of the concrete.
If this alkalinity is lost through carbonation or if
chlorides are present which can break down this
immunity, then corrosion can occur. Obviously, when
cover is low, the onset of corrosion will be sooner.
Typical Appearance
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Concrete Deterioration
S.No Deterioration Mode
9
Shrinkable Aggregates:
10
Typical Appearance
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Concrete Deterioration
S.No Deterioration Mode
11
Poor Quality Construction:
12
Typical Appearance
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Concrete Deterioration
S.No Deterioration Mode
13
Patch Accelerated Corrosion
Commonly referred to as "ring anode corrosion" or "halo
effect", patch accelerated corrosion is a phenomenon
specific to concrete restoration projects. When repairs
are completed on corrosion-damaged structures, abrupt
changes in the concrete surrounding the reinforcing steel
are created. Typical concrete repair procedures call for
removal of the concrete around the full circumference of
the reinforcing steel within the repair area, cleaning of
corrosion by-products from the steel, and refilling the
cavity with new chloride-free, high pH concrete. This
procedure leaves the reinforcing steel embedded in
adjacent environments with abruptly different corrosion
potentials. This difference in corrosion potential (voltage)
is the driving force for new corrosion sites to form in the
surrounding contaminated concrete. The evidence of
this activity is the presence of new concrete spalling
adjacent to previously completed patch repairs.
Typical Appearance
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Visual Observations
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When sufficient chloride ions (from deicing salts or from sea water)
have penetrated to the reinforcement or when the pH of the pore
solution drops to low values due to carbonation, the protective film
is destroyed and the reinforcing steel is depassivated.
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CAUSES OF CORROSION
Following are the two most common contributing factors leading to reinforcement
corrosion:
(i) Localized breakdown of the passive film on the steel by chloride ions called
chloride attack.
(ii) General breakdown of passivity by neutralization of the concrete, predominantly
by reaction with atmospheric carbon dioxide called carbonation.
CARBONATION
Carbon dioxide, which is present in the air at around 0.3 per cent by volume,
dissolves in water to form a mildly acidic solution. This forms within the pores of the
concrete, here it reacts with the alkaline calcium hydroxide forming insoluble
calcium carbonate. The pH value then drops from more than 12 to about 8.5.
In the case of carbonation, atmospheric carbon dioxide (CO2) reacts with pore
water alkali according to the generalized reaction,
Ca(OH)2 + CO2 CaCO3 + H2O
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CAUSES OF CORROSION
It consumes alkalinity and reduces pore water pH to the 89 range, where steel is
no longer passive.
The carbonation process moves as a front through the concrete, on reaching the
reinforcing steel, the passive layer decays when the pH value drops below 10.5. If
the carbonated front penetrates sufficiently deeply into the concrete to intersect
with the concrete reinforcement interface, protection is lost and, since both oxygen
and moisture are available, the steel is likely to corrode.
CHLORIDE
The passivity provided by the alkaline conditions can also be destroyed by the
presence of chloride ions, even though a high level of alkalinity remains in the
concrete. The chloride ion can locally de-passivate the metal and promote active
metal dissolution. Chlorides react with the calcium aluminate and calcium
aluminoferrite in the concrete to form insoluble calcium chloroaluminates and
calcium chloroferrites in which the chloride is bound in non-active form. However,
the reaction is never complete and some active soluble chloride always remains in
equilibrium in the aqueous phase in the concrete. It is this chloride in solution that
is free to promote corrosion of the steel.
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MECHANISM OF CORROSION
The corrosion process that takes place in concrete is electrochemical in nature.
Corrosion will result in the flow of electrons between anodic and cathodic sites on
the rebar. Concrete, when exposed to wet and dry cycles, has sufficient
conductivity to serve as an electrolyte.
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MECHANISM OF CORROSION
The corrosion of steel in concrete in the presence of oxygen but without chlorides
takes place in several steps:
At the anode, iron is oxidized to the ferrous state and releases electrons
Fe
Fe2+ + 2e-
These electrons migrate to the cathode where they combine with water and oxygen
to form hydroxyl ions
2e- + H2O + 1/2O2
Fe2+ + 2OH-
2OHFe(OH)2
In the presence of water and oxygen, the ferrous hydroxide is further oxidized to
form Fe2O3
4Fe(OH)2 + O2 + H2O
2Fe(OH)3
4Fe(OH)3
Fe2O3.2H2O
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MECHANISM OF CORROSION
At the anode, iron reacts with chloride ions to form an intermediate soluble
ironchloride complex
Fe + 2Cl-
When the ironchloride complex diffuses away from the bar to an area with higher
pH and concentration of oxygen, it reacts with hydroxyl ions to form Fe(OH) 2. This
complex reacts with water to form ferrous hydroxide.
(Fe2+ + 2Cl-) + 2H2O + 2e-
The hydrogen ions then combine with electrons to form hydrogen gas
2H+ + 2e-
H2
As in the case of corrosion of steel without chlorides, the ferrous hydroxide, in the
presence of water and oxygen, is further oxidized to form Fe 2O3
4Fe(OH)2 + O2 + H2O
2Fe(OH)3
4Fe(OH)3
Fe2O3.2H2O
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Carbonation
Chloride Contamination
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Corrosion Progress
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American Concrete Institute recommends the following limits for chloride in new
constructions (ACI 222R-01)
Category
Prestressed
Concrete
Water Soluble
ASTM C 1152
ASTM C 1218
Soxhlet
0.08
0.06
0.06
RCC
in
Conditions
Wet
0.10
0.08
0.08
RCC
in
conditions
dry
0.20
0.15
0.15
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Very severe attack: When the sulphate content is over 2 percent in soil, or
over 10,000 ppm in water, ASTM Type V cement plus a pozzolanic admixture
shall be used, with less than a 0.45 water/cement ratio.
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Aggregate
Curing conditions
Corrosion inhibitors
Cathodic protection
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M+
+ e(soluble salt) (electron)
2H+
+
2e-
(hydrogen ions (gas)
H2
in solution)
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Test/Method
Rebound Hammer
Windsor Probe
Ultrasonic Pulse Velocity
Core
Capo
Pull out
Combination
Flexural Strength
Break-off
Direct Tensile Strength
Pull Off
Concrete
quality, Ultrasonic Pulse Velocity
Homogenity, Honeycombing, Pulse Echo
Voids
Endoscopy
Gamma ray radiography
Damages Fire/Blast
Rebound Hammer
Ultrasonic Pulse Velocity
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Parameter
Test/Method
Cracks Pavements/Water Tanks Ultrasonic Pulse Velocity
Acoustic Crack detector
Dye Penetration Test
X Ray Radiography
Gamma Ray Radiography
Thermal Imaging
Crack Scope
Steel
Location, Cover, Size
Rebar locator, Bar-sizer
Corrosion
Half-Cell Potential
Resistivity
Carbonation
Chloride Content
Condition
Endoscope/Boroscope
Integrity & Performance
Tapping
Pulse echo
Acoustic Emission
Radar
Petrography
Load Tests
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S.No.
Electrical
Resistivity
(KiloOhm cm)
Corrosion
Condition
> - 200
Low
> 20
Negligible
- 350 to - 200
Intermediate
10 to 20
Low
< - 350
High
5 to 10
High
< - 500
Severe
<5
Very High
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Condition
Passive
Active or passive
Active
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Natural Draft Cooling Towers at a station operating on seawater with 35000 ppm
chloride were found to be suffering from corrosion induced damages such as spalling
of concrete, rusted reinforced bars, cracks on the concrete, delaminated concrete,
etc.
Half-cell potential values 165 to 550 mv Vs. Cu/CuSO4 - severe corrosion of
reinforcement bars)
Resistivity values - 0.4 26 kiloohms.cm - severe corrosion of rebars
Chloride content - 0.03 to 0.8% by weight of cement- high chloride
contamination of concrete
pH values lie between 8.0 to 12.5 - some chemical attack on concrete.
Rebound hammer & core tests - some deterioration of concrete strength.
Repairs were carried out to some racker columns. Inspection after about 2 years
indicated that cracks/spalling at the point of repairs had resurfaced indicating
normal patch repairs to chloride contaminated concrete are not successful and
more protective measures such as cathodic protection would be necessary for
ensuring durability of the structures.
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S.No Test
Results
Criteria
Remarks
Visual
observations
Corrosion
damages to RCC
structures. Less
damage at
Coated portions.
Rebound
CT (N) 10-19 MPa
Hammer Test CT 1 (S) 14-42 MPa
CT 2 (E) 14-26 MPa
CT 2 (W) 17-23 MPa
> 30 MPa
Lower portions
have better
compressive
strength
Half Cell
(-) 165 to (-) 550
Potential Test
More negative
than (-) 350 MV
90% Probability of
Corrosion
Most of the
readings are
more negative
than (-) 200 MV
Electrical
Resistivity
>20 no corrosion
< 5 Severe Corr.
Mostly corrosive
Carbonation
Chloride
content
Good concrete
< 0.15%
Major cause
CP best option
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26.05.09
08.05.11
01.07.12
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26.05.09
08.05.11
01.07.12
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Condition of NDCTS
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Condition of NDCTS
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Condition of NDCTS
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Condition of NDCTS
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Condition of NDCTS
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Condition of NDCTS
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RCC structures such as Bottom Ash Hopper, ESP, Ash Slurry sump, etc at a station
operating on seawater with 35000 ppm chloride were found to be suffering from
corrosion induced damages such as spalling of concrete, rusted reinforced bars,
cracks on the concrete, delaminated concrete, etc.
Half-cell potential values: 382 to 556 mv Vs. Cu/CuSO4 - severe corrosion of
reinforcement bars;
Resistivity values: 1.8 9.2 kiloohms.cm - severe corrosion of rebars;
Rebound hammer & core tests: some deterioration of concrete strength.
Patch repairs have been carried out to some of these damages and the repairs are
under observation.
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22
30
27
-457
-444
-408
15
30
28
-455
-434
-411
30
28
17
-426
-436
-423
4.4
1.9
2.8
High Corrosion
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46
52
-382
-402
-417
48
48
-425
-395
-435
47
46
-410
-457
-415
1.8
2.8
2.4
2.3
2.1
High Corrosion
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45
35
45
26
35
38
25
48
-557
-441
-409
-522
-498
-432
-514
-458
-465
7.9
6.2
7.3
9.4
7.0
High Corrosion
Condition Assessment data
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(plant uses sulphuric acid for pH/alkalinity control in the cooling water system). It was
inferred that most of the damages were on account of carbonation/chemical attack.
Repairs have been suggested and are expected to be undertaken shortly.
Subsequently anti-corrosive coatings for complete structure which are water or water
vapour touched, to be applied for further protection.
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A station in coastal region and using seawater as cooling water with about 40000
ppm chloride reported severe damages to RCC structures of induced draft cooling
towers in less than 3 years time.
Visual observations indicated that generally efflorescence (salt deposition) was
prevalent on the structures and it appeared the concrete had high porosity, some
places rust spots could be observed, a few places reinforcements were exposed,
some surface cracks were also seen. On one CT Salt along with coal dust was
deposited on the roof surface. Some expansion joints were found to be leaking. The
observations are depicted in following photographs.
The half-cell potential values: 242 to 489 mv Vs Cu/CuSO4 for older towers
for a new tower the value was +9 mv.
Chloride contamination: 0.1 to 0.9 % of the weight of concrete (acceptable
value is < 0.03%) for the older towers.
Negligible carbonation
Severe corrosion induced damages are taking place on the older towers
whereas the new tower (yet to be put in operation) is not yet under durance
from chloride. Cathodic Protection for older towers & PU coating for Tower
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A large void (such as a horizontal arch or a vertical rathole) that forms within the body of the
stored material and later collapses, resulting in a significant dynamic load on the silo walls.
Non-uniform pressures acting on a circular silo wall that are used by an off-center channel in
the material adjacent to the Wall.
Local peak pressure at a point where a funnel flow channel intersects a silo wall.
Development of mass flow in a silo structurally designed for funnel flow.
Migration of moisture from wet to dry particles within the stored solids, which causes the dry
particles to expand and imposes strong radial loads on a silo.
Variation in operating practices in emptying the silos from design.
Variation in the quality of fly ash being stored
Asymmetric pressures caused by inserts (such as beams) across the cylinder section
of a silo. (In present case some modifications had been carried out in the silo, this
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Cathodic Protection (CP): In cathodic protection, the corroding anodic areas of steel are
made cathodic by the supply of electrons from an anode applied either to the concrete
surface or embedded. There are two ways of applying cathodic protection to structures:
Galvanic and Impressed Current CP
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These two generic categories can be further subdivided into anodic, cathodic and ambiodic
(mixed) inhibitors depending upon the formulation of the inhibitor.
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Three generic types of Surface Treatment are available for the decoration and protection of
concrete surfaces, designed to control chemical ingress as well as moisture movement. They
are described as follows:
Pore-liners these are hydrophobic impregnation treatments such as silicone
impregnants, which line the pores of concrete. They repel water and therefore
prevent it from entering the concrete, but continue to allow water vapour to escape.
Pore blockers these are materials that partially or completely block the in
concrete. They may accomplish this by either reacting with the concrete to produce
pore-blocking products or by physically blocking the pores.
Film-formers these are coating systems based on either organic resins such as
styrene butadiene and acrylic copolymers or inorganic resins such as potassium
silicate, which form a protective/decorative film on the surface of the concrete.
Coatings may be endowed with special properties, such as the ability to bridge moving cracks
whilst maintaining film integrity.
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neither of the corrosion inhibitors evaluated in this study, using the specified
repairs and exposed to the specific environments, provided any corrosioninhibiting benefit.
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BS EN 1504: Products and Systems for the protection and repair of concrete
structures Definitions, requirements, quality control and evaluation of conformity
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t0 = the time for the environment to penetrate into the concrete to a level where corrosion starts
t1 = the time for the corrosion rate to increase to significant levels
t2 = the time for cracking to occur, and a subsequent further increase in corrosion rate
t3 = the time for significant structural distress to be caused
t0 will depend on quality of concrete and corrosive environment present
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CONCRETE COVER
65-80 mm.
65-80 mm.
55-70 mm.
40-50 mm.
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CONCRETE MODIFIERS
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INHIBITORS
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For 95% (of bridge decks) the epoxy coating will debond
from the steel before the chloride arrives and thus provides no
additional service life.
Epoxy Coated Rebars are not a cost effective corrosion
protection system for bridge decks in Virginia. Thus their use
should be discontinued
Virginia Transportation Research Council - 1997
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CONCRETE COATINGS
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e-
Electron Flow
e-
Current Flow
e-
Current Flow
Electrolyte ( Ionic Flow )
OH-
OHOH-
H+
OH
OH-
e-
OH-
OH-
OH-
OH-
OHCathode
Electron Flow
Current
Flow
e-
eAnode
Cation Flow
Anion Flow
OHCathode
Current
Flow
H+
0H
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Positive Connection
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Shotcrete Overlay
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Anode Mesh
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Ribon Anodes
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FHWA - 1982
UK CONCRETE SOCIETY - 1989
NACE RP0290-90 - 1990
NACE RP0390-90 - 1990
ACI 222 R- 01
BS 7361 - 1991
European Union Standard pr EN 12696-1 2000
124
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125
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126
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System type
Owner
JUPC, KSA
Sharq, KSA
Kayan, KSA
NCP, KSA
Yansab, KSA
GPIC, Bahrain
Dubai, UAE
SCECO, KSA
SCECO, KSA
HPCL, Mumbai
127
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Conclusions
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Conclusions
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130